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Theoretical study on the reaction CX 3 + SiH(CH 3 ) 3 (X = H, F)
Author(s) -
Zhang Hui,
Yang Liu,
Liu JingYao,
Li ZeSheng
Publication year - 2011
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21964
Subject(s) - chemistry , hydrogen atom abstraction , reaction rate constant , quantum tunnelling , transition state theory , atomic physics , hydrogen , computational chemistry , thermodynamics , physics , quantum mechanics , kinetics , organic chemistry
Theoretical investigations are carried out on the multiple‐channel reactions, CH 3 + SiH(CH 3 ) 3 → products and CF 3 + SiH(CH 3 ) 3 → products. The minimum energy paths (MEP) are calculated at the MP2/6‐311 + G(d,p) level, and energetic information is further refined by the MC‐QCISD (single point) method. The rate constants for major reaction channels are calculated by the canonical variational transition state theory (CVT) with small‐curvature tunneling (SCT) correction over the temperature range 200–1500 K. The theoretical rate constants are in good agreement with the available experimental data and are found to be k 1a ( T ) = 1.93 × 10 −24 T 3.15 exp(−1214.59/ T ) and k 2a ( T ) = 1.33 × 10 −25 T 4.13 exp(−397.94/ T ) (in unit of cm 3 molecule −1 s −1 ). Our calculations indicate that hydrogen abstraction channel from SiH group is the major channel due to the smaller barrier height among five channels considered. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011